EP0790274A1 - Expandable moulding composition - Google Patents

Expandable moulding composition Download PDF

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Publication number
EP0790274A1
EP0790274A1 EP97101411A EP97101411A EP0790274A1 EP 0790274 A1 EP0790274 A1 EP 0790274A1 EP 97101411 A EP97101411 A EP 97101411A EP 97101411 A EP97101411 A EP 97101411A EP 0790274 A1 EP0790274 A1 EP 0790274A1
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EP
European Patent Office
Prior art keywords
polymer
molding composition
sulfoxide
weight
temperature
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Granted
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EP97101411A
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German (de)
French (fr)
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EP0790274B1 (en
Inventor
Helmut Scheckenbach
Axel Dr. Schönfeld
Siegfried Weis
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Ticona GmbH
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Hoechst AG
Ticona GmbH
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/02—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by the reacting monomers or modifying agents during the preparation or modification of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/0204—Polyarylenethioethers
    • C08G75/0286—Chemical after-treatment
    • C08G75/0295—Modification with inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/18—Polysulfoxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/06—Polysulfones; Polyethersulfones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/22—Thermoplastic resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers

Definitions

  • the invention relates to a foamable molding composition based on a mixture of polymers containing sulfoxide groups and a high-temperature-resistant polymer, a process for producing foam by thermal treatment of the molding composition and the use thereof.
  • Polymer compositions are usually foamed by adding a low molecular weight blowing agent to the polymer composition, which releases gaseous cleavage products when heated.
  • a low molecular weight blowing agent to the polymer composition, which releases gaseous cleavage products when heated.
  • Polymers that are resistant to high temperatures are generally very difficult to foam with these conventional blowing agents because the temperature conditions are difficult to control.
  • a molding composition ie a mixture of a thermally stable plastic, in particular a thermoplastically processable high-temperature-resistant polymer, easily forms a foam with polymers which contain sulfoxide groups.
  • the polymer containing sulfoxide groups decomposes under the action of heat, whereby gases are formed which lead to the foaming of the polymer mass.
  • the high temperature resistant polymer is, for example, a thermoplastic, a high-performance plastic or a high-performance polymer.
  • Such polymers are, for example, polyether sulfones, polyarylene sulfides, polyetherimides, polyarylates, polyaryl ether ketones, polycarbonates, cycloolefin copolymers (COC), polyimides, polyamideimides, liquid-crystalline polymers (LCP), fluoropolymers, polyarylene ethers or mixtures thereof.
  • the molding composition generally contains B) 1 to 99% by weight (based on the total polymer content of the molding composition), preferably 1 to 50% by weight, in particular 3 to 20% by weight, of a polymer containing sulfoxide groups.
  • the arylenes are based, for example, on mono- or polynuclear aromatic compounds which can be unsubstituted or mono- or polysubstituted. Examples of these are phenylene, biphenylene (-C 6 H 4 -C 6 H 4 -), naphthalene, anthracene or phenanthrene. Substituents are e.g. B.
  • C 1 -C 20 hydrocarbon radicals such as C 1 -C 10 alkyl radicals, preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-hexyl or C 6 - C 14 - aryl radicals, preferably phenyl or naphthyl or also halogens, sulfonic acid, amino, nitro, cyano, hydroxyl, alkyloxy or carboxyl groups.
  • C 1 -C 10 alkyl radicals preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-hexyl or C 6 - C 14 - aryl radicals, preferably phenyl or naphthyl or also halogens, sulfonic acid, amino, nitro, cyano, hydroxyl, alkyloxy or carboxyl groups
  • Preferred polymers containing sulfoxide groups are polyarylene sulfide sulfoxides and polyarylene sulfoxides, in particular polyphenylene sulfide sulfoxide and polyphenylene sulfoxide, which, for. B. can be easily prepared by partial or complete oxidation of the sulfur groups of polyarylene sulfides with ozone or NO 2 / N 2 O 4 .
  • a sulfoxide proportion (based on all sulfur-containing bridges in the polymer) proves to be favorable at least 50%, especially at least 95%.
  • polyarylene sulfide sulfoxides are also understood as polyarylene sulfoxide and are included in the term polyarylene sulfoxide.
  • the polyarylene sulfoxides can also contain proportions of sulfone groups.
  • the production of the polymers containing sulfoxide groups is described, for example, in German patent applications DE 4314735, DE 4314736, DE 4440010 and DE 19531163, to which reference is made.
  • High-performance polymers are understood to mean plastics which have a melting point above 100 ° C., in particular above 200 ° C. These are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, VCH Verlagsgesellschaft mbH, Weinheim-New York 1992: organic fluoropolymers, Volume A11, pp. 393-430; Polyamides, Volume A21, pp. 179-206; Polycarbonate, Volume A21, pp.207-216; Polyester, Volume A21, pp. 227-252; Polyimide, Volume A21, pp. 253-273; Polymer Blends, Volume A21, pp. 274-305; High Temperature Resistant Polymers, Volume A21, pp.
  • Polycarbonates are described, for example, in "Encyclopedia of Polymer Science and Engineering, John Wiley & Sons, New York 1988, Vol. 11, pp. 648-718", to which reference is made.
  • Cycloolefin copolymers are described in H. Cherdron, M. Brekner and F. Osan, The Applied Macromolecular Chemistry (223), 121, (1994) what is referred to.
  • the molding composition or a mixture which contains at least one high-temperature-resistant polymer and at least one polymer containing sulfoxide groups can be converted into a plastic foam from a temperature of at least 300 ° C.
  • the invention thus also relates to a process for producing a foam by heating a mixture or molding composition which contains at least one high-temperature-resistant polymer and at least one polymer containing sulfoxide groups to a temperature of at least 300 ° C.
  • the time of exposure to heat is generally 5 to 60 minutes, preferably 5 to 30 minutes.
  • the foaming effect which can be achieved depends on the type of polymer containing sulfoxide groups, in particular on the amount of sulfoxide groups and on the proportion of polymer containing sulfoxide groups in the polymer mixture. In addition, the foaming effect depends on the melt viscosity of the high-temperature-resistant polymer to be foamed and on the processing temperature.
  • the heating of the mixture or the molding composition for the purpose of foaming is generally carried out in a temperature range from 300 ° C to 470 ° C.
  • the temperature range depends on the structure of the polymer containing sulfoxide groups used and on the melting point of the polymer to be foamed (high temperature-resistant polymer) and can therefore also outside the temperature range mentioned, for. B. below 300 ° C, ie up to about 250 ° C.
  • the foam formation temperature is preferably in the range from 300 ° C to 350 ° C.
  • mixtures or blends of different high-temperature resistant polymers can also be used as the high-temperature-resistant polymer
  • mixtures of different polymers containing sulfoxide groups can also be used as the polymer containing sulfoxide groups.
  • the mixtures or molding compositions according to the invention can contain customary additives, such as thermal stabilizers, UV stabilizers, antistatic agents, flame retardants, dyes, pigments, inorganic and / or organic fillers (powder, fibers, etc.) or lubricant additives such as molybdenum disulfide, graphite or polytetrafluoroethylene.
  • customary additives such as thermal stabilizers, UV stabilizers, antistatic agents, flame retardants, dyes, pigments, inorganic and / or organic fillers (powder, fibers, etc.) or lubricant additives such as molybdenum disulfide, graphite or polytetrafluoroethylene.
  • the polymer containing sulfoxide groups it is advantageous for the polymer containing sulfoxide groups to be distributed as finely and uniformly as possible in the mixture or molding composition. This is achieved, for example, by using fine powders of the components. It is also possible to mix well by thermal processing, e.g. with commercially available kneaders or extruders, preferably twin-screw extruders, at temperatures at which the polymer to be foamed melts. The multiphase blend formed in this way can then be processed into pellets, granules or powders which have no separation of the individual powder components and thus enable uniform processing.
  • an unfoamed molding compound when using polyphenylene sulfoxide (sulfoxide content at least 95%), an unfoamed molding compound can first be produced at temperatures below 300 ° C. This unfoamed molding compound can then be thermally treated above 300 ° C in one Foam, ie transfer into a foamed molding compound or a foamed mold.
  • the foam formed generally has a density which is at least 50 percent lower than that of the non-foamed material.
  • the polymers containing sulfoxide groups in particular those which do not melt at the processing temperatures, should likewise be used as the finest possible powder in order to achieve a uniform foam.
  • the average grain sizes of the polymers A) and B) used are in the range from around 0.3 to 500 ⁇ m, preferably from 5 to 300 ⁇ m, in particular from 5 to 100 ⁇ m.
  • the average molecular weight of the polymers containing sulfoxide groups is generally in the range from 4,000 to 200,000 g / mol, preferably from 10,000 to 150,000 g / mol, in particular from 25,000 to 100,000 g / mol .
  • the molding composition according to the invention as such as well as the foam produced therefrom can be used for the production of molded parts.
  • the molding compound is placed in a closed mold, foamed therein and the desired molded part formed is removed from the mold.
  • a foam with a dense, closed outer skin integral foam is formed from the molding compound by heating, from which a molded part is then produced by mechanical treatment (cutting, sawing or the like).
  • the molded parts can be used as heavy-duty functional components, for example in aircraft construction, in automobile construction and in electronics. Further uses of the molded parts can be found in chemical apparatus engineering on.
  • the foams or molded parts can also serve as heat and temperature resistant insulation materials.
  • polyphenylene sulfoxide 54.08 g of polyphenylene sulfide (®Fortron 0205 B4, Hoechst AG) were suspended in 300 ml of 99% dichloroacetic acid and 1 g of 95 to 97% sulfuric acid at 25 ° C. 46 g of N 2 O 4 were then added dropwise at a rate of 1 ml / minute and the mixture was stirred at 50 ° C. for a further 2 hours, the polyphenylene sulfoxide formed dissolving after about 20 minutes. Excess N 2 O 4 partially outgassed while stirring. Residual N 2 O 4 in the solution was expelled using a capillary with nitrogen gas at 50 ° C. for 1 hour.
  • the solution was mixed with 4 liters of demineralized water with vigorous stirring and the product was filtered off and dried.
  • the ESCA analysis of the product showed that about 98% of the sulfur groups in the polyphenylene sulfide used had been converted to sulfoxide groups (polyphenylene sulfoxide with a sulfoxide content of around 98%).
  • the density of the polyphenylene sulfoxide was 1.40 g / cm 3 .
  • the polyphenylene sulfoxide from Example 1 used in Examples 2 to 8 and the high-performance polymer used were each finely ground. 2 - 7.
  • a powder mixture of the commercially available high-temperature-resistant polymer A) and polyphenylene sulfoxide B) was placed in an aluminum dish (4.0 cm ⁇ 4.0 cm) and treated in a closed oven at the times and temperatures indicated.
  • a foam was formed with a dense, closed outer skin (integral foam). The density of the foam formed and of the polymer used are given in the table. The foams each showed the expected temperature resistance of the polymers used. example 2nd 3rd 4th 5 6 7 Comp.
  • ®Vectra A 950 liquid crystalline polyester from Hoechst AG, Frankfurt, Germany
  • 10 parts by weight of polyphenylene sulfoxide were mixed in a twin-screw kneader (type: LSM 30.34 from Leistritz GmbH, Nuremberg, Germany) at 280 ° C melt temperature without foaming, the Vectra being melted while the polyphenylene sulfoxide was not melted.
  • the molding compound was then granulated and dried. This granulate was then processed into a foam on a press of the Polystat 200 S type from Schwabenthau, Berlin. For this purpose, approx.
  • 61 g of the granulated mixture were placed in a cylindrical shape (diameter: 120 mm), the height of which was variably adjustable (height-adjustable lid by play fit).
  • the filled mold was placed under the press and heated to approx. 300 ° C. This temperature was kept at a pressure of 8 bar for 25 minutes. The mold was then cooled and the foamed molding was removed.
  • the product had a closed surface and a density of 0.55 g / cm 3 (for comparison: density of Vectra A950 is 1.40 g / cm 3 ).

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)

Abstract

Expandable moulding materials (I) contains (A) high temperature-resistant polymer(s), (B) 1-99 wt% (based on total polymer content) polymer(s) with sulphoxide groups and optionally (C) conventional additives. Also claimed is the production of foamed materials (II) by heating (I) to 300-470 degrees C. Preferably material (I) contains 1-50(preferably 3-20) wt% polymer (B) containing at least one polyarylene sulphoxide unit of formula -arylene-SO-, especially polyphenylene sulphoxide, sulphide-sulphoxide or sulphide- sulphoxide-sulphone, with a sulphoxide content (based on all sulphur-containing bridges) of at least 50 (preferably at least 95) wt% and an average molecular weight (Mw) of 4000-200000, preferably 10000-150000, especially 25000-100000. Polymer (A) is a thermoplastic, preferably a polyether-sulphone, polyarylate, polyarylene sulphide, polyether-imide, cyclo-olefin copolymer, polycarbonate or poly(aryl-ether-ketone). Components (A) and (B) have average particle sizes of 0.3-500 (preferably 5-100) microns. Additives (C) comprise thermal and UV stabilisers, antistatics, fire retardants, dyes, pigments, inorganic and/or organic fillers or lubricants.

Description

Die Erfindung betrifft eine verschäumbare Formmasse auf Basis einer Mischung aus Sulfoxidgruppen enthaltenden Polymeren und einen hochtemperaturbeständigen Polymer, ein Verfahren zur Herstellung von Schaumstoff durch thermische Behandlung der Formmasse sowie deren Verwendung.The invention relates to a foamable molding composition based on a mixture of polymers containing sulfoxide groups and a high-temperature-resistant polymer, a process for producing foam by thermal treatment of the molding composition and the use thereof.

Üblicherweise werden Polymermassen geschäumt, indem der Polymermasse ein niedermolekulares Blähmittel zugesetzt wird, das in der Hitze gasförmige Abspaltprodukte freisetzt. Hochtemperaturbeständige Polymere lassen sich mit diesen herkömmlichen Blähmitteln in der Regel aber nur sehr schlecht aufschäumen, weil die Temperaturbedingungen schwer steuerbar sind.Polymer compositions are usually foamed by adding a low molecular weight blowing agent to the polymer composition, which releases gaseous cleavage products when heated. Polymers that are resistant to high temperatures are generally very difficult to foam with these conventional blowing agents because the temperature conditions are difficult to control.

Es bestand daher die Aufgabe, die genannten Nachteile zu vermeiden.The object was therefore to avoid the disadvantages mentioned.

Die Erfindung betrifft eine verschäumbare Formmasse, die

  • A) mindestens ein hochtemperaturbeständiges Polymer,
  • B) mindestens ein Sulfoxidgruppen enthaltendes Polymer in einer Menge von 1 bis 99 Gew.-% (bezogen auf den Gesamt-Polymeranteil der Formmasse) und
  • C) gegebenenfalls übliche Additive enthält.
The invention relates to a foamable molding compound which
  • A) at least one high temperature-resistant polymer,
  • B) at least one polymer containing sulfoxide groups in an amount of 1 to 99% by weight (based on the total polymer content of the molding composition) and
  • C) optionally contains conventional additives.

Es wurde überraschend gefunden, daß eine Formmassen, d.h. eine Mischung von einem thermisch stabilen Kunststoff, insbesondere von einem thermoplastisch verarbeitbarem hochtemperaturbeständigen Polymer, mit Polymeren, die Sulfoxidgruppen enthalten, leicht einen Schaum bildet. Unter der Einwirkung von Hitze zersetzt sich das Sulfoxidgruppen enthaltende Polymer, wobei Gase entstehen, die zum Aufschäumen der Polymermasse führen.It has surprisingly been found that a molding composition, ie a mixture of a thermally stable plastic, in particular a thermoplastically processable high-temperature-resistant polymer, easily forms a foam with polymers which contain sulfoxide groups. The polymer containing sulfoxide groups decomposes under the action of heat, whereby gases are formed which lead to the foaming of the polymer mass.

Das hochtemperaturbeständige Polymer ist beispielweise ein Thermoplast, ein Hochleistungskunststoff oder Hochleistungspolymer. Derartige Polymere sind beispielsweise Polyethersulfone, Polyarylensulfide, Polyetherimide, Polyarylate, Polyaryletherketone, Polycarbonate, Cycloolefincopolymere (COC), Polyimide, Polyamidimide, flüssigkristalline Polymere (LCP), Fluorpolymere, Polyarylenether oder Mischungen davon.The high temperature resistant polymer is, for example, a thermoplastic, a high-performance plastic or a high-performance polymer. Such polymers are, for example, polyether sulfones, polyarylene sulfides, polyetherimides, polyarylates, polyaryl ether ketones, polycarbonates, cycloolefin copolymers (COC), polyimides, polyamideimides, liquid-crystalline polymers (LCP), fluoropolymers, polyarylene ethers or mixtures thereof.

Die Formmasse enthält im allgemeinen B) 1 bis 99 Gew.-% (bezogen auf den Gesamt-Polymeranteil der Formmasse), vorzugsweise 1 bis 50 Gew.-%, insbesondere 3 bis 20 Gew.-%, eines Sulfoxidgruppen enthaltenden Polymers.The molding composition generally contains B) 1 to 99% by weight (based on the total polymer content of the molding composition), preferably 1 to 50% by weight, in particular 3 to 20% by weight, of a polymer containing sulfoxide groups.

Unter Sulfoxidgruppen enthaltenden Polymeren werden Polymere oder Oligomere verstanden, die wenigstens eine Arylensulfoxid - Einheit (-Ar-SO-; Ar = Arylen) enthalten. Den Arylenen liegen beispielsweise ein- oder mehrkernige aromatische Verbindungen zugrunde, die unsubstituiert oder ein- oder mehrfach substituiert sein können. Beispiele hierfür sind Phenylen, Biphenylen (-C6H4-C6H4-), Naphthalen, Anthracen oder Phenanthren. Substituenten sind z. B. geradkettige, cyclische oder verzweigte C1 - C20 - Kohlenwasserstoffreste, wie C1 - C10 - Alkylreste, vorzugsweise Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, t-Butyl, n-Hexyl oder C6 - C14 - Arylreste, vorzugsweise Phenyl oder Naphthyl oder auch Halogene, Sulfonsäure-, Amino-, Nitro-, Cyano-, Hydroxy-, Alkyloxy- oder Carboxylgruppen.Polymers containing sulfoxide groups are understood to mean polymers or oligomers which contain at least one arylene sulfoxide unit (-Ar-SO-; Ar = arylene). The arylenes are based, for example, on mono- or polynuclear aromatic compounds which can be unsubstituted or mono- or polysubstituted. Examples of these are phenylene, biphenylene (-C 6 H 4 -C 6 H 4 -), naphthalene, anthracene or phenanthrene. Substituents are e.g. B. straight-chain, cyclic or branched C 1 -C 20 hydrocarbon radicals, such as C 1 -C 10 alkyl radicals, preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-hexyl or C 6 - C 14 - aryl radicals, preferably phenyl or naphthyl or also halogens, sulfonic acid, amino, nitro, cyano, hydroxyl, alkyloxy or carboxyl groups.

Bevorzugte Sulfoxidgruppen enthaltende Polymere sind Polyarylensulfidsulfoxide und Polyarylensulfoxide, insbesondere Polyphenylensulfidsulfoxid und Polyphenylensulfoxid, die z. B. leicht durch teilweise oder vollständige Oxidation der Schwefelgruppen von Polyarylensulfiden mit Ozon oder NO2/N2O4 hergestellt werden können. Günstig erweist sich ein Sulfoxid-Anteil (bezogen auf alle Schwefel enthaltenden Brücken im Polymer) von vorzugsweise mindestens 50 %, insbesondere von mindestens 95 %. Polyarylensulfidsulfoxide werden im folgenden auch als Polyarylensulfoxide verstanden und werden von dem Begriff Polyarylensulfoxide miterfaßt. Die Polyarylensulfoxide können auch Anteile an Sulfongruppen enthalten. Die Herstellung der Sulfoxidgruppen enthaltenen Polymere ist zum Beispiel in den deutschen Patentanmeldungen DE 4314735, DE 4314736, DE 4440010 und DE 19531163 beschrieben, worauf Bezug genommen wird.Preferred polymers containing sulfoxide groups are polyarylene sulfide sulfoxides and polyarylene sulfoxides, in particular polyphenylene sulfide sulfoxide and polyphenylene sulfoxide, which, for. B. can be easily prepared by partial or complete oxidation of the sulfur groups of polyarylene sulfides with ozone or NO 2 / N 2 O 4 . A sulfoxide proportion (based on all sulfur-containing bridges in the polymer) proves to be favorable at least 50%, especially at least 95%. In the following, polyarylene sulfide sulfoxides are also understood as polyarylene sulfoxide and are included in the term polyarylene sulfoxide. The polyarylene sulfoxides can also contain proportions of sulfone groups. The production of the polymers containing sulfoxide groups is described, for example, in German patent applications DE 4314735, DE 4314736, DE 4440010 and DE 19531163, to which reference is made.

Unter Hochleistungspolymeren werden Kunststoffe verstanden, die einen Schmelzpunkt von oberhalb von 100°C, insbesondere oberhalb von 200° C, aufweisen. Diese werden beispielsweise beschrieben in Ullmann's Encyclopedia of Industrial Chemistry, 5. Auflage, VCH Verlagsgesellschaft mbH, Weinheim-New York 1992: organische Fluorpolymere, Volume A11, S. 393-430; Polyamide, Volume A21, S. 179-206; Polycarbonate, Volume A21, S.207-216; Polyester, Volume A21, S. 227-252; Polyimide, Volume A21, S. 253-273; Polymerblends, Volume A21, S. 274-305; Hochtemperaturbeständige Polymere, Volume A21, S. 449-472; Polymethylmethacrylate, Volume A21, S. 473-486; Polyphenylenoxide, Volume A21, S. 605-614; Polyurethane, Volume A21, S. 665-716 und Silikone, Volume A24, S.57-95, worauf jeweils Bezug genommen wird.High-performance polymers are understood to mean plastics which have a melting point above 100 ° C., in particular above 200 ° C. These are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, VCH Verlagsgesellschaft mbH, Weinheim-New York 1992: organic fluoropolymers, Volume A11, pp. 393-430; Polyamides, Volume A21, pp. 179-206; Polycarbonate, Volume A21, pp.207-216; Polyester, Volume A21, pp. 227-252; Polyimide, Volume A21, pp. 253-273; Polymer Blends, Volume A21, pp. 274-305; High Temperature Resistant Polymers, Volume A21, pp. 449-472; Polymethyl methacrylate, Volume A21, pp. 473-486; Polyphenylene Oxides, Volume A21, pp. 605-614; Polyurethanes, Volume A21, pp. 665-716 and Silicones, Volume A24, pp.57-95, to which reference is made in each case.

Hochleistungskunststoffe werden beispielsweise in "G.W. Becker, D. Braun: Kunststoff - Handbuch Bd. 3/3, Carl Hanser Verlag, München 1994" beschrieben, worauf Bezug genommen wird (1. Polyarylate: S. 1-53; 2. Polyarylensulfide: S. 55-140; 3. Polysulfone: S. 141-217; 4. Flüssigkristalline Polyester: S. 219-258; 5. Polyimide: S. 263-293; 6. Polyetherimide: S. 297-335; 7. Polyamidimide: S. 337-356; 8. Poly(aryletherketone): S. 359-385).High-performance plastics are described, for example, in "GW Becker, D. Braun: Plastic Handbook Vol. 3/3, Carl Hanser Verlag, Munich 1994", to which reference is made (1. Polyarylates: pp. 1-53; 2. Polyarylene sulfides: p . 55-140; 3. Polysulfones: p. 141-217; 4. Liquid crystalline polyester: p. 219-258; 5. Polyimide: p. 263-293; 6. Polyetherimide: p. 297-335; 7. Polyamideimide: Pp. 337-356; 8. Poly (aryl ether ketones): pp. 359-385).

Polycarbonate werden beispielsweise in "Encyclopedia of Polymer Science and Engineering, John Wiley & Sons, New York 1988, Vol. 11, S. 648-718" beschrieben, worauf Bezug genommen wird.Polycarbonates are described, for example, in "Encyclopedia of Polymer Science and Engineering, John Wiley & Sons, New York 1988, Vol. 11, pp. 648-718", to which reference is made.

Cycloolefin Copolymere (COC) werden beschrieben in

Figure imgb0001
H. Cherdron, M. Brekner und F. Osan, Die Angewandte Makromolekulare Chemie (223), 121, (1994)
Figure imgb0002
, worauf Bezug genommen wird.Cycloolefin copolymers (COC) are described in
Figure imgb0001
H. Cherdron, M. Brekner and F. Osan, The Applied Macromolecular Chemistry (223), 121, (1994)
Figure imgb0002
what is referred to.

Die Formmasse oder eine Mischung, die mindestens ein hochtemperaturbeständiges Polymer und mindestens ein Sulfoxidgruppen enthaltendes Polymer enthält, kann ab einer Temperatur von mindestens 300° C in einen Kunststoffschaum überführt werden.The molding composition or a mixture which contains at least one high-temperature-resistant polymer and at least one polymer containing sulfoxide groups can be converted into a plastic foam from a temperature of at least 300 ° C.

Gegenstand der Erfindung ist somit auch ein Verfahren zur Herstellung eines Schaumstoffes durch Erhitzen von einer Mischung oder Formmasse, die mindestens ein hochtemperaturbeständiges Polymer und mindestens ein Sulfoxidgruppen enthaltendes Polymer enthält, auf eine Temperatur von mindestens 300°C. Die Zeit der Hitzeeinwirkung beträgt im allgemeinen 5 bis 60 Minuten, vorzugsweise 5 bis 30 Minuten.The invention thus also relates to a process for producing a foam by heating a mixture or molding composition which contains at least one high-temperature-resistant polymer and at least one polymer containing sulfoxide groups to a temperature of at least 300 ° C. The time of exposure to heat is generally 5 to 60 minutes, preferably 5 to 30 minutes.

Der erzielbare Schäumungseffekt hängt von der Art des Sulfoxidgruppen enthaltenden Polymers, insbesondere von der Menge der Sulfoxidgruppen ab und von dem Anteil des Sulfoxidgruppen enthaltenden Polymers in der Polymer-Mischung. Außerdem ist der Schäumungseffekt von der Schmelzviskosität des zu verschäumenden hochtemperaturbeständigen Polymers und von der Verarbeitungstemperatur abhängig.The foaming effect which can be achieved depends on the type of polymer containing sulfoxide groups, in particular on the amount of sulfoxide groups and on the proportion of polymer containing sulfoxide groups in the polymer mixture. In addition, the foaming effect depends on the melt viscosity of the high-temperature-resistant polymer to be foamed and on the processing temperature.

Das Erhitzen der Mischung oder der Formmasse zum Zweck der Schäumung erfolgt im allgemeinen in einem Temperaturbereich von 300°C bis 470°C. Der Temperaturbereich hängt von der Struktur des verwendeten Sulfoxidgruppen enthaltenden Polymers sowie vom Schmelzpunkt des zu verschäumenden Polymers (hochtemperaturbeständiges Polymer) ab und kann daher auch außerhalb des genannten Temperaturbereiches, z. B. unterhalb 300°C, d.h. bis ca. 250°C, liegen. Bei Verwendung von Polyphenylensulfoxid (Sulfoxid-Anteil mindestens 95 %) liegt die Schaumbildungstemperatur vorzugsweise im Bereich von 300°C bis 350°C.The heating of the mixture or the molding composition for the purpose of foaming is generally carried out in a temperature range from 300 ° C to 470 ° C. The temperature range depends on the structure of the polymer containing sulfoxide groups used and on the melting point of the polymer to be foamed (high temperature-resistant polymer) and can therefore also outside the temperature range mentioned, for. B. below 300 ° C, ie up to about 250 ° C. When using polyphenylene sulfoxide (sulfoxide content at least 95%) the foam formation temperature is preferably in the range from 300 ° C to 350 ° C.

Gemäß der Erfindung können als hochtemperaturbeständiges Polymer auch Mischungen oder Blends verschiedener hochtemperaturbeständiger Polymere und als Sulfoxidgruppen enthaltendes Polymer auch Mischungen verschiedener Sulfoxidgruppen enthaltenden Polymere eingesetzt werden.According to the invention, mixtures or blends of different high-temperature resistant polymers can also be used as the high-temperature-resistant polymer, and mixtures of different polymers containing sulfoxide groups can also be used as the polymer containing sulfoxide groups.

Die Mischungen oder Formmassen gemäß der Erfindung können übliche Additive enthalten, wie thermische Stabilisatoren, UV-Stabilisatoren, Antistatika, Flammschutzmittel, Farbstoffe, Pigmente, anorganische und/oder organische Füllstoffe (Pulver, Fasern u.s.w.) oder Gleitmittelzusätze wie Molybdändisulfid, Graphit oder Polytetrafluorethylen. Bei Verwendung von üblichen Mengen ergibt sich keine Beeinträchtigung der physikalischen oder mechanischen Eigenschaften der gebildeten Schäume.The mixtures or molding compositions according to the invention can contain customary additives, such as thermal stabilizers, UV stabilizers, antistatic agents, flame retardants, dyes, pigments, inorganic and / or organic fillers (powder, fibers, etc.) or lubricant additives such as molybdenum disulfide, graphite or polytetrafluoroethylene. When using conventional amounts there is no impairment of the physical or mechanical properties of the foams formed.

Zur Herstellung des Schaumes ist es zweckmäßig, daß das Sulfoxidgruppen enthaltende Polymer möglichst fein und gleichmäßig in der Mischung oder Formmasse verteilt ist. Dies wird beispielsweise durch Verwendung feiner Pulver der Komponenten erreicht. Es besteht auch die Möglichkeit, eine gute Vermischung durch eine thermische Verarbeitung, z.B. mit handelsüblichen Knetern oder Extrudern, vorzugsweise Zweiwellenextrudern, bei Temperaturen, bei denen das zu verschäumende Polymer aufschmilzt, zu erzielen. Das dabei gebildete mehrphasige Blend kann dann zu Pellets, Granulat oder Pulver verarbeitet werden, die keine Entmischung der einzelnen Pulver-Komponenten aufweisen und somit eine gleichmäßige Verarbeitung ermöglichen.To produce the foam, it is advantageous for the polymer containing sulfoxide groups to be distributed as finely and uniformly as possible in the mixture or molding composition. This is achieved, for example, by using fine powders of the components. It is also possible to mix well by thermal processing, e.g. with commercially available kneaders or extruders, preferably twin-screw extruders, at temperatures at which the polymer to be foamed melts. The multiphase blend formed in this way can then be processed into pellets, granules or powders which have no separation of the individual powder components and thus enable uniform processing.

So kann zum Beispiel bei Verwendung von Polyphenylensulfoxid (Sulfoxid-Anteil mindestens 95 %) zunächst eine ungeschäumte Formmasse bei Temperaturen unterhalb von 300°C hergestellt werden. Diese ungeschäumte Formmasse läßt sich dann durch thermische Behandlung oberhalb von 300°C in einen Schaumstoff, d.h. in eine geschäumte Formmasse oder ein geschäumtes Formte überführen.For example, when using polyphenylene sulfoxide (sulfoxide content at least 95%), an unfoamed molding compound can first be produced at temperatures below 300 ° C. This unfoamed molding compound can then be thermally treated above 300 ° C in one Foam, ie transfer into a foamed molding compound or a foamed mold.

Der gebildete Schaumstoff weist im allgemeinen eine gegenüber dem unverschäumten Material um mindestens 50 Prozent verringerte Dichte auf.The foam formed generally has a density which is at least 50 percent lower than that of the non-foamed material.

Die Sulfoxidgruppen enthaltenden Polymere, insbesondere solche, die bei den Verarbeitungstemperaturen nicht aufschmelzen, sollten ebenfalls als möglichst feines Pulver eingesetzt werden, um einen gleichmäßigen Schaum zu erzielen.The polymers containing sulfoxide groups, in particular those which do not melt at the processing temperatures, should likewise be used as the finest possible powder in order to achieve a uniform foam.

Im allgemeinen liegen die mittleren Korngrößen der eingesetzten Polymere A) und B) im Bereich von um 0,3 bis 500 µm, vorzugsweise von 5 bis 300 µm, insbesondere von 5 bis 100 µm.In general, the average grain sizes of the polymers A) and B) used are in the range from around 0.3 to 500 μm, preferably from 5 to 300 μm, in particular from 5 to 100 μm.

Das mittlere Molekulargewicht der Sulfoxidgruppen enthaltenden Polymere, ausgedrückt als Gewichtsmittel MW, liegt im allgemeinen im Bereich von 4 000 bis 200 000 g/mol, bevorzugt von 10 000 bis 150 000 g/mol, insbesondere von 25 000 bis 100 000 g/mol.The average molecular weight of the polymers containing sulfoxide groups, expressed as weight average M W , is generally in the range from 4,000 to 200,000 g / mol, preferably from 10,000 to 150,000 g / mol, in particular from 25,000 to 100,000 g / mol .

Die Formmasse gemäß der Erfindung als solche ebenso wie der daraus hergestellte Schaumstoff können zur Herstellung von Formteilen verwendet werden. Im ersten Fall wird die Formmasse in eine geschlossene Form gegeben, darin aufgeschäumt und das gewünschte gebildete Formteil der Form entnommen. Im zweiten Fall wird aus der Formmasse durch Erhitzen ein Schaum mit einer dichten, geschlossenen Außenhaut (Integralschaum) gebildet, aus dem dann durch mechanische Behandlung (schneiden, sägen o.a.) ein Formteil hergestellt wird.The molding composition according to the invention as such as well as the foam produced therefrom can be used for the production of molded parts. In the first case, the molding compound is placed in a closed mold, foamed therein and the desired molded part formed is removed from the mold. In the second case, a foam with a dense, closed outer skin (integral foam) is formed from the molding compound by heating, from which a molded part is then produced by mechanical treatment (cutting, sawing or the like).

Die Formteile können als hochbeanspruchbare Funktionsbauteile, beispielsweise im Flugzeugbau, im Automobilbau und der Elektronik, verwendet werden. Weitere Verwendungen der Formteile bieten sich im chemischen Apparatebau an. Die Schäume oder Formteile können auch als wärme- und temperaturbeständige Isolationsmaterialien dienen.The molded parts can be used as heavy-duty functional components, for example in aircraft construction, in automobile construction and in electronics. Further uses of the molded parts can be found in chemical apparatus engineering on. The foams or molded parts can also serve as heat and temperature resistant insulation materials.

Vorteile des erfindungsgemäßen Verfahrens zur Herstellung schaumförmiger hochtemperaturbeständiger Polymere sind darin zu sehen, daß

  • kein Zusatz von niedermolekularen Treibmitteln notwendig ist,
  • das Verfahren mit einfachen technischen Mitteln durchführbar ist,
  • Schäume mit besonders geringer Dichte möglich sind
  • und daß ein breiter Bereich des Schäumungsgrades und der Porengröße einstellbar sind.
Advantages of the process according to the invention for the production of foam-like, high temperature-resistant polymers can be seen in that
  • no addition of low molecular weight blowing agents is necessary,
  • the process can be carried out using simple technical means,
  • Foams with a particularly low density are possible
  • and that a wide range of the degree of foaming and the pore size are adjustable.

Beispiele:Examples:


1. Herstellung von Polyphenylensulfoxid:
54,08 g Polyphenylensulfid (®Fortron 0205 B4, Hoechst AG) wurden in 300 ml 99%-iger Dichloressigsäure und 1 g 95 bis 97 %-iger Schwefelsäure bei 25°C suspendiert. Anschließend wurden unter Rühren 46 g N2O4 mit einer Tropfgeschwindigkeit von 1 ml/Minute zugetropft und für weitere 2 Stunden bei 50°C gerührt, wobei nach etwa 20 Minuten das gebildete Polyphenylensulfoxid in Lösung ging. Überschüssiges N2O4 gaste zum Teil während des Rührens aus. Restliches N2O4 in der Lösung wurde mit Hilfe einer Kapillare mit Stickstoffgas für 1 Stunde bei 50°C ausgetrieben. Zur Ausfällung des Produktes wurde die Lösung mit 4 Liter entsalztem Wasser unter starkem Rühren vermischt und das Produkt abfiltriert und getrocknet. Die ESCA-Analyse des Produktes ergab, daß ca. 98 % der Schwefelgruppen des eingesetzten Polyphenylensulfids zu Sulfoxidgruppen umgewandelt worden sind (Polyphenylensulfoxid mit Sulfoxid-Anteil um 98 %). Die Dichte des Polyphenylensulfoxid betrug 1,40 g/cm3.
Das in den Beispielen 2 bis 8 verwendete Polyphenylensulfoxid aus Beispiel 1 und das eingesetzte Hochleistungspolymer wurden jeweils fein gemahlen.
2 - 7. In eine Aluminiumschale (4,0 cm x 4,0 cm) wurde eine Pulvermischung aus dem kommerziell erhältlichen hochtemperaturbeständigen Polymer A) und Polyphenylensulfoxid B) gefüllt und in einem geschlossenen Ofen bei den angegebenen Zeiten und Temperaturen behandelt. Dabei bildete sich jeweils ein Schaum mit einer dichten, geschlossenen Außenhaut (Integralschaum). Die Dichte des gebildeten Schaumes und des eingesetzten Polymers sind in der Tabelle angegeben. Die Schäume zeigten jeweils die erwartete Temperaturbeständigkeit der eingesetzten Polymere. Beispiel 2 3 4 5 6 7 Komp. A) Ultrason E2010 Ultrason S2010 Ultem 1010 Makrolon 2600PC Apec HT KU 1-9351 PEEK 450 G Menge [g] 10,3 13 12 13 13 13 Komp. B) Menge [g] 1,8 2,3 1,8 2,5 3,0 3,5 Schäumtemperatur [°C] 325 325 325 325 325 450 Zeit [min] 13 11 20 10 10 13 Dichte Schaum [g/cm3] 0,59 0,23 0,58 0,27 0,25 0,55 Dichte A) [g/cm3] 1,37 1,24 1,27 1,2 1,15 1,30 ®Ultrason = Polyethersulfon der Firma BASF AG, Ludwigshafen, Deutschland
®Ultem = Polyetherimid der Firma General Electric, Rüsselsheim, Deutschland
®Makrolon = Polycarbonat der Firma Bayer AG, Leverkusen, Deutschland
®Apec = Polyacrylat der Firma Bayer AG, Leverkusen, Deutschland
®PEEK = Polyetheretherketon der Firma Victrex Deutschland GmbH, Hofheim.
8. 90 Gewichtsteile ®Vectra A 950 (Flüssigkristalliner Polyester der Fa. Hoechst AG, Frankfurt, Deutschland) und 10 Gewichtsteile Polyphenylensulfoxid wurden in einem Zweiwellenkneter (Typ: LSM 30.34 der Fa. Leistritz GmbH, Nürnberg, Deutschland) bei 280°C Massetemperatur ohne Schaumbildung miteinander vermischt, wobei das Vectra aufgeschmolzen wurde, während das Polyphenylensulfoxid nicht aufschmolz. Anschließend wurde die Formmasse granuliert und getrocknet. Dieses Granulat wurde anschließend auf einer Presse des Typs Polystat 200 S der Fa. Schwabenthau, Berlin zu einem Schaum verarbeitet. Hierzu wurden ca. 61 g der granulierten Mischung in eine zylindrische Form (Durchmesser: 120 mm) gegeben, deren Höhe variabel einstellbar war (Deckel in Höhe verschiebbar durch Spielpassung). Die gefüllte Form wurde unter die Presse gestellt und auf ca. 300°C geheizt. Diese Temperatur wurde 25 Minuten lang gehalten bei einem Druck von 8 bar. Anschließend wurde die Form abgekühlt und der geschäumte Formkörper entnommen. Das Produkt hatte eine geschlossene Oberfläche und eine Dichte von 0,55 g/cm3 (zum Vergleich: Dichte von Vectra A950 ist 1,40 g/cm3).
1. Production of polyphenylene sulfoxide:
54.08 g of polyphenylene sulfide (®Fortron 0205 B4, Hoechst AG) were suspended in 300 ml of 99% dichloroacetic acid and 1 g of 95 to 97% sulfuric acid at 25 ° C. 46 g of N 2 O 4 were then added dropwise at a rate of 1 ml / minute and the mixture was stirred at 50 ° C. for a further 2 hours, the polyphenylene sulfoxide formed dissolving after about 20 minutes. Excess N 2 O 4 partially outgassed while stirring. Residual N 2 O 4 in the solution was expelled using a capillary with nitrogen gas at 50 ° C. for 1 hour. To precipitate the product, the solution was mixed with 4 liters of demineralized water with vigorous stirring and the product was filtered off and dried. The ESCA analysis of the product showed that about 98% of the sulfur groups in the polyphenylene sulfide used had been converted to sulfoxide groups (polyphenylene sulfoxide with a sulfoxide content of around 98%). The density of the polyphenylene sulfoxide was 1.40 g / cm 3 .
The polyphenylene sulfoxide from Example 1 used in Examples 2 to 8 and the high-performance polymer used were each finely ground.
2 - 7. A powder mixture of the commercially available high-temperature-resistant polymer A) and polyphenylene sulfoxide B) was placed in an aluminum dish (4.0 cm × 4.0 cm) and treated in a closed oven at the times and temperatures indicated. A foam was formed with a dense, closed outer skin (integral foam). The density of the foam formed and of the polymer used are given in the table. The foams each showed the expected temperature resistance of the polymers used. example 2nd 3rd 4th 5 6 7 Comp. A) Ultrason E2010 Ultrason S2010 Ultem 1010 Makrolon 2600PC Apec HT KU 1-9351 PEEK 450 G. Amount [g] 10.3 13 12th 13 13 13 Comp. B) amount [g] 1.8 2.3 1.8 2.5 3.0 3.5 Foaming temperature [° C] 325 325 325 325 325 450 Time [min] 13 11 20th 10th 10th 13 Dense foam [g / cm 3 ] 0.59 0.23 0.58 0.27 0.25 0.55 Density A) [g / cm 3 ] 1.37 1.24 1.27 1.2 1.15 1.30 ®Ultrason = polyethersulfone from BASF AG, Ludwigshafen, Germany
®Ultem = polyetherimide from General Electric, Rüsselsheim, Germany
®Makrolon = polycarbonate from Bayer AG, Leverkusen, Germany
®Apec = polyacrylate from Bayer AG, Leverkusen, Germany
®PEEK = polyether ether ketone from Victrex Deutschland GmbH, Hofheim.
8. 90 parts by weight of ®Vectra A 950 (liquid crystalline polyester from Hoechst AG, Frankfurt, Germany) and 10 parts by weight of polyphenylene sulfoxide were mixed in a twin-screw kneader (type: LSM 30.34 from Leistritz GmbH, Nuremberg, Germany) at 280 ° C melt temperature without foaming, the Vectra being melted while the polyphenylene sulfoxide was not melted. The molding compound was then granulated and dried. This granulate was then processed into a foam on a press of the Polystat 200 S type from Schwabenthau, Berlin. For this purpose, approx. 61 g of the granulated mixture were placed in a cylindrical shape (diameter: 120 mm), the height of which was variably adjustable (height-adjustable lid by play fit). The filled mold was placed under the press and heated to approx. 300 ° C. This temperature was kept at a pressure of 8 bar for 25 minutes. The mold was then cooled and the foamed molding was removed. The product had a closed surface and a density of 0.55 g / cm 3 (for comparison: density of Vectra A950 is 1.40 g / cm 3 ).

Claims (16)

Verschäumbare Formmasse, enthaltend A) mindestens ein hochtemperaturbeständiges Polymer, B) mindestens ein Sulfoxidgruppen enthaltendes Polymer in einer Menge von 1 bis 99 Gew.-% (bezogen auf den Gesamtpolymeranteil der Formmasse) und C) gegebenenfalls übliche Additive. Foamable molding compound, containing A) at least one high temperature-resistant polymer, B) at least one polymer containing sulfoxide groups in an amount of 1 to 99% by weight (based on the total polymer content of the molding composition) and C) if appropriate, conventional additives. Formmasse nach Anspruch 1, dadurch gekennzeichnet, daß die Komponente B) in einer Menge von vorzugsweise 1 bis 50 Gew.-%, insbesondere 3 bis 20 Gew.-% eingesetzt wird.Molding composition according to claim 1, characterized in that component B) is used in an amount of preferably 1 to 50% by weight, in particular 3 to 20% by weight. Formmasse nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß das Sulfoxidgruppen enthaltende Polymer wenigstens eine Polyarylensulfoxid-Einheit der Formel -(Ar-SO-; Ar = Arylen) enthält.Molding composition according to claim 1 or 2, characterized in that the polymer containing sulfoxide groups contains at least one polyarylene sulfoxide unit of the formula - (Ar-SO-; Ar = arylene). Formmasse nach einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß als Sulfoxidgruppen enthaltendes Polymer Polyphenylensulfoxid, Polyphenylensulfidsulfoxid oder Polyphenylensulfidsulfoxidsulfon eingesetzt wird.Molding composition according to one or more of claims 1 to 3, characterized in that polyphenylene sulfoxide, polyphenylene sulfide sulfoxide or polyphenylene sulfide sulfoxide sulfone is used as the polymer containing sulfoxide groups. Formmasse nach einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß der Sulfoxid-Anteil der Komponente B) (bezogen auf alle Schwefel enthaltenden Brücken im Polymer) vorzugsweise mindestens 50 Gew.-%, insbesondere mindestens 95 Gew.-% beträgt.Molding composition according to one or more of claims 1 to 4, characterized in that the sulfoxide content of component B) (based on all sulfur-containing bridges in the polymer) is preferably at least 50% by weight, in particular at least 95% by weight. Formmasse nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß das hochtemperaturbeständige Polymer ein Thermoplast ist.Molding composition according to one or more of claims 1 to 5, characterized in that the high temperature-resistant polymer is a thermoplastic. Formmasse nach einem oder mehreren der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß als hochtemperaturbeständiges Polymer A) ein Polyethersulfon, ein Polyarylat, ein Polyarylensulfid, ein Polyetherimid, ein Cycloolefincopolymer, ein Polycarbonat oder ein Poly(aryletherketon) eingesetzt wird.Molding composition according to one or more of claims 1 to 6, characterized in that a polyether sulfone, a polyarylate, a polyarylene sulfide, a polyetherimide, a cycloolefin copolymer, a polycarbonate or a poly (aryl ether ketone) is used as the high temperature-resistant polymer A). Formmasse nach einem oder mehreren der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß die mittlere Korngröße der Komponente A) bzw. B) im Bereich von 0,3 bis 500 µm, vorzugsweise 5 bis 300 µm und insbesondere 5 bis 100 µm liegt.Molding composition according to one or more of claims 1 to 7, characterized in that the average grain size of component A) or B) is in the range from 0.3 to 500 µm, preferably 5 to 300 µm and in particular 5 to 100 µm. Formmassen nach einem oder mehreren der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß das mittlere Molekulargewicht Mw der Komponenten B) im Bereich von 4000 bis 200 000 g/mol, vorzugsweise 10 000 bis 150 000 g/mol und insbesondere 25 000 bis 100 000 g/mol liegt.Molding compositions according to one or more of Claims 1 to 8, characterized in that the average molecular weight M w of components B) is in the range from 4000 to 200,000 g / mol, preferably 10,000 to 150,000 g / mol and in particular 25,000 to 100 000 g / mol. Formmassen nach einem oder mehreren der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß als übliche Additive thermische Stabilisatoren, UV-Stabilisatoren, Antistatika, Flammschutzmittel, Farbstoffe, Pigmente, anorganische und/oder organische Füllstoffe oder Gleitmittelzusätze eingesetzt werden.Molding compositions according to one or more of claims 1 to 9, characterized in that thermal stabilizers, UV stabilizers, antistatic agents, flame retardants, dyes, pigments, inorganic and / or organic fillers or lubricant additives are used as customary additives. Verfahren zur Herstellung eines Schaumstoffs, dadurch gekennzeichnet, daß eine Formmasse, die A) mindestens ein hochtemperaturbeständiges Polymer, B) mindestens ein Sulfoxidgruppen enthaltendes Polymer in einer Menge von 1 bis 99 Gew.-% (bezogen auf den Gesamtpolymeranteil der Formmasse) und C) gegebenenfalls übliche Additive enthält, auf eine Temperatur im Bereich von 300°C bis 470°C erhitzt wird.A process for producing a foam, characterized in that a molding composition which comprises A) at least one high-temperature-resistant polymer, B) at least one polymer containing sulfoxide groups in an amount of 1 to 99% by weight (based on the total polymer content of the molding composition) and C) optionally contains conventional additives, is heated to a temperature in the range from 300 ° C to 470 ° C. Verfahren nach Anspruch 11, dadurch gekennzeichnet, daß die Temperatur im Bereich von 300°C bis 350°C liegt.A method according to claim 11, characterized in that the temperature is in the range of 300 ° C to 350 ° C. Verfahren nach Anspruch 11 oder 12, dadurch gekennzeichnet, daß das Erhitzen in einer Zeit von 5 bis 60 Minuten, vorzugsweise 5 bis 30 Minuten durchgeführt wird.A method according to claim 11 or 12, characterized in that the heating is carried out in a time of 5 to 60 minutes, preferably 5 to 30 minutes. Verfahren nach einem oder mehreren der Ansprüche 11 bis 13, dadurch gekennzeichnet, daß der gebildete Schaumstoff eine um mindestens 50 Prozent gegenüber dem unverschäumten Material verringerte Dichte aufweist.Method according to one or more of claims 11 to 13, characterized in that the foam formed has a density which is reduced by at least 50 percent compared to the non-foamed material. Verwendung der Formmasse gemäß einem oder mehreren der Ansprüche 1 bis 10 oder des Schaumstoffs hergestellt nach einem oder mehreren der Ansprüche 11 bis 14 zur Herstellung von Formteilen.Use of the molding composition according to one or more of claims 1 to 10 or of the foam produced according to one or more of claims 11 to 14 for the production of molded parts. Verwendung nach Anspruch 15 zur Herstellung von temperaturbeständigen Isolationsmaterialien.Use according to claim 15 for the production of temperature-resistant insulation materials.
EP97101411A 1996-02-14 1997-01-30 Expandable moulding compositions Expired - Lifetime EP0790274B1 (en)

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DE19605359A DE19605359A1 (en) 1996-02-14 1996-02-14 Plastic foams and processes for their production
DE19605359 1996-02-14

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US6566353B2 (en) * 1996-12-30 2003-05-20 Bone Care International, Inc. Method of treating malignancy associated hypercalcemia using active vitamin D analogues
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US20070149629A1 (en) * 2005-12-22 2007-06-28 Michael Stephen Donovan Expanded and expandable high glass transition temperature polymers
US10815354B2 (en) 2014-09-30 2020-10-27 Sekisui Plastics Co., Ltd. Bead expanded molded article, resin expanded particles, method for producing resin expanded particles, expandable resin particles and method for producing bead expanded molded article
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US5786397A (en) 1998-07-28
CN1168902A (en) 1997-12-31
JPH09227706A (en) 1997-09-02
US5708041A (en) 1998-01-13
DE59711454D1 (en) 2004-05-06
DE19605359A1 (en) 1997-08-21
KR970061984A (en) 1997-09-12

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